Cyclometallation of Platinum Group Elements: Between Complexes and Organometallics

A special issue of Crystals (ISSN 2073-4352). This special issue belongs to the section "Organic Crystalline Materials".

Deadline for manuscript submissions: closed (11 January 2024) | Viewed by 3170

Special Issue Editor


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Guest Editor
Department of Analytical Chemistry and Applied Spectroscopy, Uniwersytet Mikołaja Kopernika w Toruniu, 87 100 Torun, Poland
Interests: metal complexes; 15N NMR; 2-arylpyridines; Au(III) complexes; Pd(II) complexes; Pt(II) complexes

Special Issue Information

Dear Colleagues,

Many organic ligands, especially of the heterocyclic type, coordinate transition metal ions using N,C- or P,C-chelating mode. While the formation of metal–nitrogen or metal–phosphorus bonds involves an electron lone pair present at the N or P atom, the metal–carbon bond is usually created following the deprotonation of the respective CHn moiety. This is why the obtained metal–organic compounds contain both M–N or M–P and M–C bonds, so they can be regarded as either metal complexes or organometallics. In the geometrical sense, such chelation processes result in the occurrence of the ring system with participation of the metal atom and are thus often called cyclometallation.

The above-described cyclometallated compounds are abundant for platinide group metals—in the broad sense of this meaning, i.e., including not only palladium and platinum, but also ruthenium, rhodium, osmium, and iridium. These species form single crystals suitable for X-ray analysis relatively easily; moreover, as the central Pd(II), Pd(IV), Pt(II), Pt(IV), Ru(II), Rh(III), Os(II), and Ir(III) central ions are diamagnetic, they can be studied via NMR spectroscopy. A large number of studies for such compounds have been carried out during the last few decades, and that number is increasing from year to year because of various applications, related mainly to biological or catalytic activity and luminescent properties.

The scope of this Special Issue covers research on synthesis, X-ray, and spectroscopic studies as well as potential applications of the cyclometallated Pd, Pt, Ru, Rh, Os, and Ir compounds with various N,C- and P,C-chelating organic ligands. Review papers are also welcomed.

Prof. Dr. Leszek Pazderski
Guest Editor

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Keywords

  • platinum group metals
  • cyclometallation
  • palladium complexes
  • platinum complexes
  • ruthenium complexes
  • rhodium complexes
  • osmium complexes
  • iridium complexes

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Published Papers (2 papers)

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Research

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11 pages, 5412 KiB  
Article
Dioxin-Linked Covalent Organic Framework-Supported Palladium Complex for Rapid Room-Temperature Suzuki–Miyaura Coupling Reaction
by Allea Campbell, Ziad Alsudairy, Chaochao Dun, Fazli Akram, Kayla Smith-Petty, Abrianna Ambus, Danielle Bingham, Tandabany Dinadayalane, Conrad Ingram and Xinle Li
Crystals 2023, 13(8), 1268; https://doi.org/10.3390/cryst13081268 - 17 Aug 2023
Cited by 3 | Viewed by 1714
Abstract
Covalent organic framework (COF)-supported palladium catalysts have garnered enormous attention for cross-coupling reactions. However, the limited linkage types in COF hosts and their suboptimal catalytic performance have hindered their widespread implementation. Herein, we present the first study immobilizing palladium acetate onto a dioxin-linked [...] Read more.
Covalent organic framework (COF)-supported palladium catalysts have garnered enormous attention for cross-coupling reactions. However, the limited linkage types in COF hosts and their suboptimal catalytic performance have hindered their widespread implementation. Herein, we present the first study immobilizing palladium acetate onto a dioxin-linked COF (Pd/COF-318) through a facile solution impregnation approach. By virtue of its permanent porosity, accessible Pd sites arranged in periodic skeletons, and framework robustness, the resultant Pd/COF-318 exhibits exceptionally high activity and broad substrate scope for the Suzuki–Miyaura coupling reaction between aryl bromides and arylboronic acids at room temperature within an hour, rendering it among the most effective Pd/COF catalysts for Suzuki–Miyaura coupling reactions to date. Moreover, Pd/COF-318 demonstrates excellent recyclability, retaining high activity over five cycles without significant deactivation. The leaching test confirms the heterogeneity of the catalyst. This work uncovers the vast potential of dioxin-linked COFs as catalyst supports for highly active, selective, and durable organometallic catalysis. Full article
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Review

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69 pages, 3015 KiB  
Review
Pd(II), Pd(III) and Pd(IV) Cyclometallated Compounds with 2-Arylpyridines and Their Derivatives or Analogues: 44 Years (1980–2023) of NMR and Single Crystal X-ray Studies
by Leszek Pazderski and Pavel A. Abramov
Crystals 2023, 13(10), 1482; https://doi.org/10.3390/cryst13101482 - 11 Oct 2023
Viewed by 1220
Abstract
In this paper, a review on Pd(II), Pd(III), and Pd(IV) cyclometallated compounds with 2-arylpyridines (2-phenylpyridine, 2-benzylpyridine, 2-benzoylpyridine, 2-phenoxypyridine, 2-phenylsulfanylpyridine, 2-anilinopyridine, 2-(naphth-1-yl)pyridine, 2-(naphth-2-yl)pyridine, and their derivatives) and their analogues (2-phenylquinoline and 7,8-benzoquinoline) with 174 references is presented. A total of 672 species, containing κ [...] Read more.
In this paper, a review on Pd(II), Pd(III), and Pd(IV) cyclometallated compounds with 2-arylpyridines (2-phenylpyridine, 2-benzylpyridine, 2-benzoylpyridine, 2-phenoxypyridine, 2-phenylsulfanylpyridine, 2-anilinopyridine, 2-(naphth-1-yl)pyridine, 2-(naphth-2-yl)pyridine, and their derivatives) and their analogues (2-phenylquinoline and 7,8-benzoquinoline) with 174 references is presented. A total of 672 species, containing κ2-N(1),C(6′)*-palladium (Pd(II), Pd(III), Pd(IV)) or analogous moiety (i.e., chelated by nitrogen of the pyridine-like ring and the deprotonated ortho-carbon of the phenyl-like ring) and thus possessing a character intermediate between metal complexes and organometallics, studied in the years 1980–2023 by NMR spectroscopy and/or single crystal X-ray diffraction (202 X-ray structures, for 186 species), are described. The biological or catalytic activity and luminescence properties of these species, as well as their possible applications as advanced materials were studied and are also quoted. Full article
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